In this paper, we report on the synthesis of poly(phenylenevinylene)s containing m-linked phenylene groups in order to reduce the length of conjugation, which is an important tool to influence the color of photo- and electroluminescence. Various substituted and unsubstituted divinylbenzenes and 4,4'-divinylbiphenyl were synthesized as monomers. These were polymerized via diene metathesis condensation, acyclic diene metathesis (ADMET), using the fluorinated Schrock-type initiator [Mo(=NAr)(=C(H)CMe3)O(Me(CF3)(2))(2)]; (Ar = 2,6-diisopropyl-phenyl). The neat poly(phenylenevinylene)s suffer from a very low solubility. To overcome this problem, substituents were introduced into the monomers, and copolymerization was performed with exo, exo-norbornene-2,3-dioldiacetate. The polymers were characterized by H-1-NMR, FT-m, UV/VIS and GPC analysis. Photoluminescence (PL) spectra were taken and used to evaluate the photophysical properties of the oligomers and copolymers, which showed solid-state PL-quantum efficiencies of up to 52%.